475561-48-9Relevant academic research and scientific papers
Remarkable activity of a novel cyclic seleninate ester as a glutathione peroxidase mimetic and its facile in situ generation from allyl 3-hydroxypropyl selenide
Back, Thomas G.,Moussa, Ziad
, p. 12104 - 12105 (2002)
1,2-Oxaselenolane Se-oxide is a novel cyclic seleninate ester that functions as a remarkably efficient glutathione peroxidase mimetic by catalyzing the reduction of tert-butyl hydroperoxide to tert-butyl alcohol in the presence of benzyl thiol. The seleni
Diselenides and Allyl Selenides as Glutathione Peroxidase Mimetics. Remarkable Activity of Cyclic Seleninates Produced in Situ by the Oxidation of Allyl ω-Hydroxyalkyl Selenides
Back, Thomas G.,Moussa, Ziad
, p. 13455 - 13460 (2007/10/03)
A series of aliphatic diselenides and selenides containing coordinating substituents was tested for glutathione peroxidase (GPx)-like catalytic activity in a model system in which the reduction of tert-butyl hydroperoxide with benzyl thiol to afford dibenzyl disulfide and tert-butyl alcohol was performed under standard conditions and monitored by HPLC. Although the diselenides showed generally poor catalytic activity, allyl selenides proved more effective. In particular, allyl 3-hydroxypropyl selenide (25) rapidly generated 1,2-oxaselenolane Se-oxide (31) in situ by a series of oxidation and [2,3]sigmatropic rearrangement steps. The remarkably active cyclic seleninate 31 proved to be the true catalyst, reacting with the thiol via a postulated mechanism in which the thioseleninate 32 is first produced, followed by further thiolysis to selenenic acid 33 and oxidation-dehydration to regenerate 31. In contrast to catalysis with GPx, formation of the corresponding selenenyl sulfide 34 comprises a competing deactivation pathway in the catalytic cycle of 31, as a separate experiment revealed that authentic 34 was a much less effective catalyst than 31. 1,2-Oxaselenane Se-oxide (37), the six-membered homologue of 31, was formed similarly from allyl 4-hydroxybutyl selenide (26), but proved a less effective catalyst than 31. Compounds 31 and 37 are the first examples of unsubstituted monocyclic seleninate esters.
